Abstract

Neutralization of the bio-oil pH has been shown to generate a neutralized bio-oil aqueous phase (NBOAP) that includes most of the acidic components and a neutralized bio-oil organic phase (NBOOP) that includes hydrophobic organics, such as phenols. NBOOP can be used for fuel production, while NBOAP can be fed to microbial electrolysis cells (MECs) for hydrogen production. After pH neutralization, some organic acidic components remain in NBOOP. This work is focused on capturing acidic compounds from NBOOP through water extraction and electrosorption, and demonstrating hydrogen production via MECs. Capacitive deionization (CDI) is proven effective in capturing ions from NBOOP-contacted water and NBOAP via electrosorption. Captured acidic compounds enable the MEC application to effectively produce renewable hydrogen. Chemical oxygen demand (COD) removal of 49.2%, 61.5%, and 60.8% for 2, 4, and 10 g/L-anode/day loading were observed, corresponding to a total COD degradation of 0.19 g/L, 0.79 g/L, and 1.3 g/L, respectively. A maximum hydrogen productivity of 4.3 L-H 2/L-anode/day was obtained. Major compounds in the water phase such as fatty acids, sugar derivatives, furanic and phenolic compounds were converted to hydrogen with an efficiency of 80–90%. Lastly, this approach may lead the entire biomass pyrolysis process to be an overall carbon-neutralmore » process.« less

@article{osti_1430619,
title = {Electrosorption of organic acids from aqueous bio-oil and conversion into hydrogen via microbial electrolysis cells},
author = {Park, Lydia Kyoung-Eun and Satinover, Scott J. and Yiacoumi, Sotira and Mayes, Richard T. and Borole, Abhijeet P. and Tsouris, Costas},
abstractNote = {Neutralization of the bio-oil pH has been shown to generate a neutralized bio-oil aqueous phase (NBOAP) that includes most of the acidic components and a neutralized bio-oil organic phase (NBOOP) that includes hydrophobic organics, such as phenols. NBOOP can be used for fuel production, while NBOAP can be fed to microbial electrolysis cells (MECs) for hydrogen production. After pH neutralization, some organic acidic components remain in NBOOP. This work is focused on capturing acidic compounds from NBOOP through water extraction and electrosorption, and demonstrating hydrogen production via MECs. Capacitive deionization (CDI) is proven effective in capturing ions from NBOOP-contacted water and NBOAP via electrosorption. Captured acidic compounds enable the MEC application to effectively produce renewable hydrogen. Chemical oxygen demand (COD) removal of 49.2%, 61.5%, and 60.8% for 2, 4, and 10 g/L-anode/day loading were observed, corresponding to a total COD degradation of 0.19 g/L, 0.79 g/L, and 1.3 g/L, respectively. A maximum hydrogen productivity of 4.3 L-H2/L-anode/day was obtained. Major compounds in the water phase such as fatty acids, sugar derivatives, furanic and phenolic compounds were converted to hydrogen with an efficiency of 80–90%. Lastly, this approach may lead the entire biomass pyrolysis process to be an overall carbon-neutral process.},
doi = {10.1016/j.renene.2018.02.076},
journal = {Renewable Energy},
number = C,
volume = 125,
place = {United States},
year = {2018},
month = {2}
}

Figures / Tables:

Figure 1: CDI cell with two half cells, each of which contains (1) a Plexiglas cover, (2) a viton gasket, (3) a titanium plate (current collector) with a carbon sheet, (4) a plastic mesh to keep the electrodes separated, and (5) a hollow middle viton gasket with syringe needles formore » input/output. Right: a picture of a carbon sheet taped to a current collector plate made of titanium.« less

In this study, furanic and phenolic compounds are problematic byproducts resulting from the decomposition of lignocellulosic biomass during biofuel production. This study assessed the capacity of a microbial electrolysis cell (MEC) to produce hydrogen gas (H 2) using a mixture of two furanic (furfural, FF; 5-hydroxymethyl furfural, HMF) and three phenolic (syringic acid, SA; vanillic acid, VA; and 4-hydroxybenzoic acid, HBA) compounds as the sole carbon and energy source in the bioanode. The rate and extent of biotransformation of the five compounds, efficiency of H 2 production, as well as the anode microbial community structure were investigated. The five compoundsmore » were completely transformed within 7-day batch runs and their biotransformation rate increased with increasing initial concentration. At an initial concentration of 1,200 mg/L (8.7 mM) of the mixture of the five compounds, their biotransformation rate ranged from 0.85 to 2.34 mM/d. The anode coulombic efficiency was 44-69%, which is comparable to wastewater-fed MECs. The H 2 yield varied from 0.26 to 0.42 g H 2-COD/g COD removed in the anode, and the bioanode volume-normalized H 2 production rate was 0.07-0.1 L/L-d. The major identified fermentation products that did not transform further were catechol and phenol. Acetate was the direct substrate for exoelectrogenesis. Current and H 2 production were inhibited at an initial substrate concentration of 1,200 mg/L, resulting in acetate accumulation at a much higher level than that measured in other batch runs conducted with a lower initial concentration of the five compounds. The anode microbial community consisted of exoelectrogens, putative degraders of the five compounds, and syntrophic partners of exoelectrogens. The H 2 production route demonstrated in this study has proven to be an alternative to the currently used process of reforming natural gas to supply H 2 needed to upgrade bio-oils to stable hydrocarbon fuels.« less

In this paper, microbial electrolysis of an aqueous phase generated from catalytic pyrolysis of pine sawdust was investigated for renewable hydrogen production. The microbial electrolysis cell (MEC) performance was investigated at an organic loading rate ranging from 2 to 50 g/L-day. A maximum hydrogen productivity of 5.8 ± 0.18 L/L-day was obtained, however, the productivity increased linearly only up to a loading rate of 10 g/L-day. The highest current density achieved was 6.8 ± 0.1 A/m 2. The efficiency of conversion of the substrate to current in the anode decreased with increasing loading, but the initial maximum Coulombic efficiency wasmore » 98 ± 0.04%. The cathode efficiency, on the other hand, increased with loading up to a maximum of 89 ± 1.4%. Total hydrogen recovery was relatively constant for most runs at 30%, which is equivalent to an yield of 0.6 moL H 2/mole COD, except at the highest loading rate. The operation of the MEC under batch mode, however, resulted in a higher hydrogen recovery of 63 ± 4%. The conversion of a wide range of compounds, including carboxylic acids, anhydrosugars, furanic and phenolic compounds present in the aqueous phase is reported. Finally, the results demonstrate potential for hydrogen production from a waste stream which can improve the total biofuel or energy yield of the biorefinery.« less

We investigated the effect of flow rate and recycle on the conversion of a biomass-derived pyrolysis aqueous phase in amicrobial electrolysis cell (MEC) to demonstrate production of renewable hydrogen in biorefinery. A continuous MEC operation was investigated under one-pass and recycle conditions usingthe complex, biomass-derived, fermentable, mixed substrate feed at a constant concentration of 0.026 g/L,while testing flow rates ranging from 0.19 to 3.6 mL/min. This corresponds to an organic loading rate (OLR) of 0.54₋10 g/L-day. Mass transfer issues observed at low flow rates were alleviated using high flow rates.Increasing the flow rate to 3.6 mL/min (3.7 min HRT) duringmore » one-pass operation increased the hydrogen productivity 3-fold, but anode conversion efficiency (ACE) decreased from 57.9% to 9.9%. Recycle of the anode liquid helped to alleviate kinetic limitations and the ACE increased by 1.8-fold and the hydrogen productivity by 1.2-fold compared to the one-pass condition at the flow rate of 3.6 mL/min (10 g/L-d OLR). High COD removal was also achieved under recycle conditions, reaching 74.2 1.1%, with hydrogen production rate of 2.92 ± 0.51 L/L-day. This study demonstrates the advantages of combining faster flow rates with a recycle process to improve rate of hydrogen production from a switchgrass-derived stream in the biorefinery.« less

Applications of bio-oil are limited by its challenging properties including high moisture content, low pH, high viscosity, high oxygen content, and low heating value. Separation of switchgrass bio-oil components by adding water, organic solvents (hexadecane and octane), and sodium hydroxide may help to overcome these issues. Acetic acid and phenolic compounds were extracted in aqueous and organic phases, respectively. Polar chemicals, such as acetic acid, did not partition in the organic solvent phase. Acetic acid in the aqueous phase after extraction is beneficial for a microbial-electrolysis-cell application to produce hydrogen as an energy source for further hydrodeoxygenation of bio-oil. Organicmore » solvents extracted more chemicals from bio-oil in combined than in sequential extraction; however, organic solvents partitioned into the aqueous phase in combined extraction. When sodium hydroxide was added to adjust the pH of aqueous bio-oil, organic-phase precipitation occurred. As the pH was increased, a biphasic aqueous/organic dispersion was formed, and phase separation was optimized at approximately pH 6. The neutralized organic bio-oil had approximately 37% less oxygen and 100% increased heating value than the initial centrifuged bio-oil. In conclusion, the less oxygen content and increased heating value indicated a significant improvement of the bio-oil quality through neutralization.« less

Despite the potential carbon-neutrality of switchgrass bio-oil, its high acidity and diverse chemical composition limit its utilization. The objectives of this research are to investigate pH neutralization of bio-oil by adding various alkali solutions in a batch system and then perform neutralization using process intensification devices, including a static mixer and a centrifugal contactor. The results indicate that sodium hydroxide and potassium hydroxide are more appropriate bases for pH neutralization of bio-oil than calcium hydroxide due to the limited solubility of calcium hydroxide in aqueous bio-oil. Mass and total acid number (TAN) balances were performed for both batch and continuous-flowmore » systems. Upon pH neutralization of bio-oil, the TAN values of the system increased after accounting the addition of alkali solution. A bio-oil heating experiment showed that the heat generated during pH neutralization did not cause a significant increase in the acidity of bio-oil. The formation of phenolic compounds during neutralization was initially suspected of increasing the system’s overall TAN value because some of these compounds (e.g., vanillic acid) act as polyprotic acids and have a stronger influence on the TAN value than monoprotic acids (e.g., acetic acid). The amount of phenolics in separated bio-oil phases, however, did not change significantly after pH neutralization. In conclusion, process intensification devices provided sufficient mixing and separation of the organic and aqueous phases, suggesting a scale-up route for the bio-oil pH neutralization process.« less